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Structure and chemical bonding of binary ytterbium germanides, Yb$$_{3}$$Ge$$_{5}$$ and YbGe$$_{3}$$, prepared by high-pressure and high-temperature reactions

高温高圧合成されたイットリウム・ゲルマニウム二元合金Yb$$_{3}$$Ge$$_{5}$$・YbGe$$_{3}$$の構造及び化学結合

原田 桃子*; 福岡 宏*; 松村 大樹; 犬丸 啓*

Harada, Momoko*; Fukuoka, Hiroshi*; Matsumura, Daiju; Inumaru, Kei*

Two new ytterbium germanides, Yb$$_{3}$$Ge$$_{5}$$ and YbGe$$_{3}$$, were obtained using high-pressure and high-temperature reactions. Yb$$_{3}$$Ge$$_{5}$$ crystallizes in the Pu$$_{3}$$Pd$$_{5}$$ structure (the space group${it Cmcm}$, No.63) with $$a$$ = 9.3739${AA}$, $$b$$ = 7.5569${AA}$, $$c$$ = 9.5170${AA}$, and $$V$$ = 674.16$AA $^{3}$$. It is a new polymorph and contains Ge$$_{5}$$ units with a square-pyramidal structure. COHP and ELF calculations revealed that the unit is constructed with strong Ge-Ge covalent bonds. The XAS analysis showed that the mean oxidation state of Yb is +2.4. It is metallic and is an example of electron-rich Zintl phases. YbGe$$_{3}$$ crystallizes in the Cu$$_{3}$$Au structure (the space group ${it Pm$overline{3}$m}$, No.221) having a unit cell of $$a$$ = 4.27${AA}$ and $$V$$ = 78.13$AA $^{3}$$. It is the first example for heavy rare-earth germanides having the Cu$$_{3}$$Au-type structure. The mean oxidation state of Yb is +2.4. YbGe$$_{3}$$ is metallic and is possibly a valence-fluctuating system.

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パーセンタイル:66.38

分野:Chemistry, Physical

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